CN107743664B - Electrochemical device for storing electrical energy - Google Patents

Electrochemical device for storing electrical energy Download PDF

Info

Publication number
CN107743664B
CN107743664B CN201680031378.5A CN201680031378A CN107743664B CN 107743664 B CN107743664 B CN 107743664B CN 201680031378 A CN201680031378 A CN 201680031378A CN 107743664 B CN107743664 B CN 107743664B
Authority
CN
China
Prior art keywords
electrode
reactor
electrodes
electrolyte
electrochemical device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201680031378.5A
Other languages
Chinese (zh)
Other versions
CN107743664A (en
Inventor
M.吉安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Global Energy Storage Co.,Ltd.
Original Assignee
Qiao Milaiman
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qiao Milaiman filed Critical Qiao Milaiman
Publication of CN107743664A publication Critical patent/CN107743664A/en
Application granted granted Critical
Publication of CN107743664B publication Critical patent/CN107743664B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4214—Arrangements for moving electrodes or electrolyte
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/029—Bipolar electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Filling, Topping-Up Batteries (AREA)
  • Secondary Cells (AREA)
  • Battery Mounting, Suspending (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

An electrochemical device for storing electrical energy, comprising: a reactor (1) equipped with a side wall (2), a top wall (3), a bottom wall (5), an electrolyte inlet (7), an electrolyte outlet (8); and a plurality of electrodes Ex, where x is an integer from 1 to n, arranged in the reactor (1), in the form of cones and frustums placed alternately and arranged with the wider portion of each electrode facing the top wall (3) or the bottom wall (5) of the reactor (1), the frustums being in contact with the side walls (2) and the apices of the cones defining an axis passing through the open area of the frustums.

Description

Electrochemical device for storing electrical energy
Technical Field
The present invention relates to an electrochemical device for storing electrical energy (electric power) and a method for storing electrical energy.
Background
There are a number of critical issues in the area of mass storage of electrical energy. It is actually necessary to have the following memory cells: it is capable of operating over a very wide range of power and capacity while simultaneously benefiting from aspects that present a small volume.
A promising way to store such electrical energy is by means of electrochemical methods. Currently, the most efficient and safest electrochemical technique is the electrolysis of non-ferrous metals in aqueous media, and more particularly, metals with high energy content such as zinc or manganese.
Furthermore, the technique is simple and cheap: it is therefore advantageous to be able to operate such electrolysis in a reversible manner.
Patent application WO 2011/015723 describes a process for the simultaneous co-generation of electrical energy and hydrogen by entirely electrochemical means. The method comprises the following steps: a stage of storing electric power (electric) by electrolysis of a solution of an electrolyzable metal and formation of an electrolyzable metal-hydrogen cell, and a stage of recovering electric power and generating hydrogen by operation of said cell.
However, in such a device, the reactor is very bulky in order to be able to supply a large amount of electrical energy.
Furthermore, for high power applications, the metal deposits are often non-uniform, which impairs the electrochemical performance of the device and may even lead to short-circuiting of the electrodes through the formation of metal dendrites.
Disclosure of Invention
It is an object of the present invention to remedy the drawbacks of the prior art and in particular to provide a device that enables the storage of large amounts of electrical energy.
This object is intended to be achieved by an electrochemical device for storing electrical energy, comprising: comprising a reactor having side walls, a top wall, a bottom wall, an electrolyte inlet, an electrolyte outlet, and a plurality of electrodes Ex, where x is an integer from 1 to n, located in the reactor, in the form of cones (cone) and frustums (truncated cone) arranged alternately and assembled in such a way that: the tapered portion of each electrode faces the top or bottom wall of the reactor, the frustum is in contact with the side wall of the reactor, and the apex of the cone defines an axis through the open area of the frustum.
The object also tends to be achieved by a method for storing electrical energy as follows: which comprises the following successive steps:
-providing the above-mentioned electrochemical device for storing electrical energy,
-performing an introduction of an electrolyte to the electrochemical device, the electrolyte comprising metal ions,
-electrically connecting the first electrode to a negative terminal of a power supply and the second electrode to a positive terminal of the power supply,
-providing electrical energy to reduce the metal ions on the electrodes of the electrochemical device to form an electrolyzable metal cell.
Drawings
Further advantages and features will become more clearly apparent from the following description of a particular embodiment of the invention, given purely by way of non-limiting example and illustrated in the accompanying drawings, in which:
figure 1 shows, in cross-section, a schematic view of a reactor of an electrochemical device according to an embodiment of the invention,
figure 2 schematically shows in cross-section an additional electrode of an electrochemical device according to the invention.
Detailed Description
The present invention relates to an electrochemical device for storing electrical energy in a direct and reversible manner.
As shown in fig. 1, the electrochemical device for storing electrical energy includes:
a reactor 1 having:
the side walls 2 are made of steel,
the top wall 3 is made of a sheet of steel,
the bottom wall 5 is made of a steel sheet,
the electrolyte inlet 7 is made up of o,
the electrolyte outlet 8 is made up of a circular ring,
-a plurality of electrodes Ex, where x is an integer from 1 to n, located in the reactor, in the form of cones and frustums arranged alternately and assembled in such a way: the tapered portion of each electrode faces the top wall 3 or the bottom wall 5 of the reactor 1, the frustum being in contact with the side wall 2, the apex of the cone defining an axis through the open area of the frustum.
The reactor 1 is preferably a closed reactor in which the electrolyte flows. The reactor 1 is, for example, a vessel. The side wall 2 is preferably circular.
The reactor 1 is closed at its top portion by a top wall 3, also called lid.
The reactor is closed at its bottom part by a bottom wall, also called bottom.
The bottom wall 5 and the top wall 3 are preferably conical in shape. The apex of the cone of the top wall 3 and the apex of the cone of the bottom wall 5 define an axis AA'.
The conical shape means that these walls present a conical surface: their surfaces are defined by straight or substantially straight curves passing through fixed points or vertices and variable points forming a closed flat curve.
The closed section preferably has a cylindrical or ovoid shape.
The cone is advantageously a cone of revolution and the side walls 2 are cylindrical, the closed cross-sections of the bottom wall 5 and the top wall 3 forming a circle corresponding to the dimensions of the side walls 2.
Advantageously, the top wall 3 is configured to form a first main electrode 4.
According to a first embodiment, the top wall 3 forms a first electrode 4.
According to another embodiment, the top wall 3 acts as a mechanical support for the first electrode 4. The first electrode 4 is advantageously supported by the reactor cover. The device is robust and simple to implement.
The first electrode 4 may be a primary anode or a primary cathode of the electrochemical device.
In a preferential mode of operation, the first electrode 4 forms the main cathode of the electrochemical device.
The first electrode 4 is then connected to the negative terminal of the DC power supply.
The cover is advantageously electrically conductive. Which is electrically connected to the negative terminal of the DC power supply to bias the first electrode immersed in the electrolyte.
The first electrode 4, which is designed to be in contact with the electrolyte, may be covered with a coating to enhance the electrochemical reaction and resistance to chemical and gas attack.
The first electrode 4 is advantageously made of a material that is not attacked by oxygen in an acidic medium. Which is covered on its surface with titanium nitride, for example, or may be made of steel coated with a conductive ceramic. The conductive ceramic is non-oxide.
Preferably, the first electrode 4 is made of stainless steel.
The bottom wall 5 is configured to form a second main electrode 6.
According to a specific embodiment, the bottom wall 5 forms a second electrode 6.
According to another embodiment, the bottom wall 5 acts as a mechanical support for the second electrode 6.
The second electrode is made of lead-coated stainless steel, for example.
Preferably, the second electrode is an anode, which forms the primary anode of the electrochemical device.
The bottom wall of the reactor 1 is electrically conductive and is biased to the potential of the positive terminal of the external power supply.
Electrode ExArranged between the bottom wall 5 and the top wall 3. Electrode ExAlso called additional electrode.
Electrode E1The additional electrode closest to the first electrode 4. Which forms a proximal (proximal) electrode with respect to the first electrode 4.
Electrode EnThe additional electrode furthest from the first electrode 4. Which forms a distal (digital) electrode with respect to the first electrode 4.
FIG. 1 shows, for example, the inclusion of four additional electrodes E1、E2、E3And E4The reactor of (1). The distal electrode is electrode E4。
Electrode ExThe amount of which depends on the electrical power required.
As shown in fig. 1, an additional electrode ExAdvantageously in the form of a full cone or frustum. The apex of the conical electrode and the opening of the electrode in the form of a frustum are aligned along an axis AA'. The apex and the opening of the cone are advantageously all oriented in the same direction.
Preferably, the apex and the opening are oriented in the direction of the top wall 3, the tapering shape of the cone or frustum being aligned in the direction of the bottom wall 5.
In one embodiment, the electrodes Ex, where x is an odd integer, are in the form of full cones and the electrodes Ex, where x is an even integer, are in the form of frustums.
Electrodes E in which x is an odd integerxSpaced from the side wall 2 of the reactor 1.
Electrodes E in which x is an even integerxIn contact with the side wall 2 of the reactor 1. The frustoconical shape of these electrodes enables fluid flow at the apex of the cone.
This embodiment is particularly efficient and compact. However, a reversed configuration is also possible.
According to a preferred embodiment, the electrolyte inlet 7 of the reactor is located in the top wall 3 forming the first electrode E1At the apex of the cone.
The electrolyte is fed into the reactor via the lid, for example by means of a volumetric pump, so that its flow rate and pressure can be controlled.
An electrolyte outlet 8 is located in the bottom part of the reactor 1 at the electrode EnAnd the bottom wall 5 of the reactor.
The electrolyte outlet 8 may be formed by one or more holes located in the bottom of the reactor 1.
As a modification, the electrolyte inlet 7 and the electrolyte outlet 8 may be reversed.
Thereby forming a flow path (schematically represented by arrows in fig. 1) for the electrolyte, said path going from the electrolyte inlet 7 to the electrolyte outlet 8, alternately electrodes E where x is an odd integerxElectrodes E arranged between and on the side walls of the reactor, where x is an even integerxPasses through the opening at the apex of the frustum of the cone.
In this embodiment, the flow of electrolyte is natural and caused by gravity.
This configuration makes it possible to obtain an excellent circulation of the electrolyte flow (flux), which is permanently renewed in front of the electrodes.
Such a completely symmetrical geometry makes it possible to deliver a suitable flow of current from one electrode to the other and enables the elimination of leakage currents.
However, as a variant, asymmetrical configurations are possible, but they are less efficient.
The control of the current flow in relation to the reduction of disturbances leads to a better homogeneity of the metal deposit.
Advantageously, the heat loss is reduced and well distributed.
Electrode ExIs believed to be floating, i.e. the total potential difference at electrode E provided by the generator between electrode 6 and electrode 3 supported by the reactorxAre naturally distributed among each of them.
The "floating potential" is applied to an electrolyte bath flowing between the electrodesBalanced in a natural way. The potential depends on the potential difference applied between the container and the reactor cover and also on the electrode ExThe number of the cells.
Preferably, as shown in FIGS. 1 and 2, an additional electrode ExIs bipolar. Bipolar refers to electrode ExCan act as both an anode and a cathode. The bipolar electrode presents two surfaces-an anode surface 9 and a cathode surface 10.
During the electrodeposition step, metal is deposited on the cathode surface and natural oxygen is formed on the anode surface.
These special electrodes are advantageously designed from materials suitable for the electrochemical conditions, in particular for bipolarity. The electrodes are made, for example, as follows: lead, tin, nickel, or titanium, with a conductive coating such as a non-oxide ceramic being advantageous for each of the materials. These ceramics are advantageously non-oxide and may be made of silicon carbide (SiC), titanium carbide (TiC), silicon nitride (Si)3N4) Titanium nitride (TiN), and the like.
The electrode may also be a hybrid bipolar electrode made from lead oxide, combined tin and lead oxide, or from a lead alloy.
Advantageously, the anode surface 9 and the cathode surface 10 are made of different materials.
The cathode surface is made of, for example, stainless steel, lead or lead oxide, which may be coated or uncoated.
Preferably, the electrical energy storage is carried out on a hybrid bipolar electrode made of tin and lead oxides.
The anode surface preferably comprises at least one metal wire wound to form a conical helix. The wire is preferably made of lead. According to another embodiment, the anode surface is covered by a second metal wire wound to form a conical spiral, said second metal wire being made of tin.
Even more preferably, the anodic surface comprises a set of metal wires, for example a cable made up of a number k of strands (strand) wound to form one or more conical spirals. This is known, for example, as a "Pappus" conical helix. This configuration results in a large growth from the exchange surface by the following factor: the coefficient is equal to pi (3.14) xk, which results in the retention of native oxide. Advantageously, no main gas is released when the electrochemical reaction takes place.
The twisted wire bundle may exhibit a cylindrical cross-section, as shown in fig. 2, or it may exhibit a star-shaped or cross-shaped cross-section.
Advantageously, the cross-section is a cylindrical cross-section.
Preferably, the wrapped bundle of metal consists of a mixture of: a wire or a tin wire made of pure lead surrounding the oxide paste of the metal. The assembly of twisted wires and oxides constituting the helix may also be covered by a shield. The shield is, for example, a membrane porous to the electrolyte that is cut to conform to the tapered shape of the electrode. Polyethylene films may be used.
Alternatively, the cable may be replaced by a braid. The braid must be manufactured in a manner that allows electrolyte to penetrate between the strands. The securing of the strands of the braid may be adjusted with a support shim that provides a slight gap between the strands.
Preferably, the angle b shown in fig. 2 (defined by the axis AA' and the centroid distance L of the cone) is greater than 45 °. Even more preferably, the angle b is greater than 50 ° to prevent the oxide from detaching from the electrode by gravity.
Advantageously, the turns of the spiral or spirals are joined to cover the anode surface 9 and to increase the amount of active material on each electrode. If necessary, several layers of cable wound in a papus spiral can be stacked one on top of the other to increase the exchange surface even further. Advantageously, on the anode, the strands of the cable are assembled at their ends by welding to each other and to the base coat of the support forming them.
Preferably, the anode surface 9 of the additional electrode Ex is covered by a coating of lead or a lead alloy and said lead coating is covered by said spiral. The lead coating may be a sheet of lead foil. A sheet of tin foil may be used instead of the lead foil.
Additional electrodes E of conical shapexIs defined by:
S＝π.L.(R+r)
wherein:
l is the distance between the centers of the edges of the cone,
r is the outer radius of the cone,
r is the inner radius of the cone,
l can be defined by L ═ r/sin b, where b is the angle at the apex of the cone, giving the following: s ═ pi. (R/sin b. (R + R).
For R0.85 m, R0.05 m and sin b 0.766, the surface of the electrode is 2.97m2。
This particular configuration of the stack of additional electrodes in the shape of a cone or frustum in a cylindrical volume creates a very large exchange surface in a very small volume.
This exchange surface is further increased by said specific configuration of the anode surface of the electrode, i.e. by the metal wire wound to form a conical spiral.
The bipolar electrode enables to completely reverse the polarity and the operation as counter electrode in the chemical attack phase when reversing the polarity and using the reactor as a generator. In the electricity generation phase, the metal deposited on the cathode surface is subjected to a chemical attack phase and an electric current is generated (battery effect).
For example, for a reactor vessel having a height H of 1.5m of about 3m2Of the surface of (2) 51 bipolar additional electrodes (for odd additional electrodes E)xElectrodes in the form of frustums and additional electrodes E for even numbersxAn electrode in the form of a full cone) the power P supplied is P E.I.
Where E53 vs × 2.85V ≈ 150V and I400A/m2×3m2The power is about 180kW, 1200A.
Advantageously, the set of bipolar additional electrodes ExThus forming a compact stack of facing electrochemical surfaces, one of said facing electrochemical surfaces acting as an anode and said facing electrochemical surfacesThe other surface of the face acts as a cathode.
During operation of the electrochemical device, the electrolyte is present at the first electrode 4 and at the electrode E in a first phase1Until it reaches the side wall 2. Then it follows the additional electrode E2Up at the electrode E1Cathode surface and electrode E2Flows between the anode surfaces. At electrode E2Through an opening at the top of the electrode and at electrode E2Cathode surface and electrode E3Until it reaches the side wall 2 and so on until it reaches the bottom of the reactor.
The combination of bipolar electrodes with a conical stack ensures a perfect distribution of the current flowing from one bipolar electrode to the other, while ensuring a precise and controlled flow by gravity of the electrolyte stream containing the chemical solution of the metal to be deposited.
Additional electrode ExAdvantageously having the same surface.
The active reaction surfaces remain uniform from one pair to the other, from the top to the outside of the bottom of the reactor, and a current isopycnic density is obtained.
Additional electrode E of the same active surfacexThe stack of (a) enables to obtain perfect control of the surface of the pairs of electrodes, which is therefore constant.
The electrode assembly enables a large reaction surface to be obtained in an extremely small size. The volume of the reactor 1 can be significantly reduced.
Such a device enables a larger amount of electrical energy to be stored compared to a device with flat electrodes for the same reactor volume.
According to a preferred embodiment, the side wall 2 of the reactor is electrically insulated to prevent electrical contact between the first electrode 4 and the second electrode 6.
The electrically insulating side wall 2 not only ensures the electrode ExAre electrically insulated from each other and ensure electrodes ExElectrically insulated from the first electrode 4 and the second electrode 6.
Advantageously, the side wall 2 of the reactor also acts as a mechanical support for the electrodes. The position of the electrodes can be equalized by means of spacers placed in the side walls 2 of the reactor.
The spacer is advantageously made of an electrically insulating material.
Electrode E in the reactorxIs for example carried out by the support of an electrically insulating ring projecting from the outer body of the reactor.
This configuration is used without any gas release (the reactor operating at atmospheric pressure), in particular in the case of direct power storage when the reactor 1 comprises lead electrodes.
Preferably, the gasket is configured so as to form an electrode ExThe top wall 3 and the bottom wall 5 are substantially parallel to each other.
In the preferred mode, two electrodes E are arranged in seriesxThe distance therebetween is substantially the same at any point along any axis parallel to axis AA'. The potential and chemical reactions are thus better distributed.
Preferably, the distance between the electrodes is comprised between 0.5cm and 1.5cm, so that the ohmic losses can be significantly reduced.
The reversible electrical energy storage method comprises the following successive steps:
-providing an electrochemical device as described in the preceding paragraphs,
-performing an introduction of an electrolyte to the electrochemical device, the electrolyte comprising metal ions,
-electrically connecting the first electrode to a negative terminal of a power supply and the second electrode to a positive terminal of the power supply,
-providing electrical energy to reduce the metal ions on the electrode to form a metal battery.
The electrolyte contains metal ions, which may be zinc, manganese or nickel ions, or they may be cadmium ions.
Preferably, the electrolyte is a sulphate-based aqueous solution.
The sulphate is a metal sulphate advantageously selected from lead, zinc, manganese or cadmium.
The first electrochemical step, i.e. energy storage, is carried out by electrodeposition of the metal in solution on the electrodes of the electrochemical device.
In a first step, metal ions in solution are reduced and the metal is deposited on the cathode of the bipolar electrode.
During the electrodeposition phase of the metal on the cathode, i.e. on the reactor wall and on the cathode surface of bipolar electrodes nested inside one another, oxygen is released at the anode.
The oxygen gas converts the metal phase of the anode surface of the bipolar electrode into an oxide.
Electrodeposition is carried out using electrical energy.
The electrical energy storage is in the form of metal deposits.
As electrodeposition of the metal occurs, the metal content of the electrolyte changes, gradually decreasing. Water containing metal sulfates can be added continuously to the electrolyte, which is also called liquor (liquor), if necessary.
After the formation of the electrolyzable metal cell, the method comprises an operating phase of the cell comprising the dissolution of the previously deposited metal to generate electrical energy.
As the chemical attack of the metal gradually occurs, the metal is again dissolved in the electrolyte. The dissolution of the metal produces hydrogen by simultaneous reduction of the oxide on the anode side to recombine into water.
The reactor has become a generator by the battery effect. Due to the large exchange surface, its internal resistance is reduced.
Electrical energy is recovered by connecting the first electrode 4 and the second electrode 6 to an electrical energy recovery system.
Preferably, the apparatus comprises an electrolyte tank connected to the electrolyte inlet 4 and the electrolyte outlet 8 of the reactor 1 to form a closed loop. The electrolyte used to form the electrolyzable metal cell is reused for the operational stages of the cell.
During the electrodeposition phase, the electrolyte is gradually stored in the storage tank. The tank then serves as a supply reserve for the electric energy production phase.
After the electrodeposition phase, i.e. after the formation of the cell, the electrolyte is advantageously drained from the reactor 1. This draining of the electrolyte means that there is no longer any possible current and the circuit is open. This operation makes it possible to avoid any self-discharge of the battery during non-use of the stored energy.
The resulting metal deposit is stable when electrolyte drains from the tank and is no longer in contact with the deposited metal. The deposit remains non-oxidizing for a very long time, essentially preserving the electrical energy it consumes during its electrodeposition.
Advantageously, the electrolyte is always drained with the apparatus switched off. This operation, which is made very easy by the configuration of the reactor, prevents the known problem of self-discharge of the electrical storage cells.
The side wall comprises a drainage means, which is advantageously located in the bottom part of the reactor. It is also possible to use double side walls, the inner walls of the two being at each electrode ExIs provided with a check valve to achieve more efficient drainage.
The electrolyte used to form the electrolytic metal cell is reused for the operational stages of the cell.
The electrolyte formed in the previous operation will flow into the closed loop again when operation as a battery occurs. The initial acid content is high and the metal content is low during this dissolution step. When dissolution occurs, the metal is dissolved again.
For example, in the case of lead, during the generation of electrical energy, the lead sulfate solution is regenerated for future reuse.
Depending on the configuration chosen, the controlled flow of the electrolyte enables direct storage of electrical energy or direct generation of electrical energy in the form of electricity.
Several reactors may be electrically connected in series or in parallel.
Preferably, the apparatus comprises at least a second reactor, the two reactors being mounted in series, the two reactors being electrically connected.
The two reactors are in fluid communication: the second reactor is located between the first reactor and the electrolyte tank, the electrolyte outlet of the first reactor is connected to the electrolyte inlet of the second reactor, and the electrolyte outlet of the second reactor is connected to the electrolyte tank.
The second reactor also includes a plurality of electrodes. The second reactor is advantageously identical to the first reactor.
Advantageously, the electrical connections for the operation of the electrochemical device are very simple to make.
The reactor is supplied by a DC generator during the energy storage phase and, during the metal dissolution phase, the reactor itself acts as a controlled generator.
During the metal electrodeposition phase, the first electrode is connected to the negative terminal of the generator, while the second electrode forming the anode is connected to the positive terminal of the generator.
When chemical attack occurs, the reactor functions as a generator. Which is then electrically connected to one or more electrical energy recovery systems.
An external DC power supply provides the external electrical energy necessary for electrodeposition and the connection that causes the direction of current flow to be reversed.
The very compact device exhibits a high active surface density in a small volume. The device, advantageously operating at a selected temperature close to ambient temperature, presents a greatly improved heat exchange coefficient and allows the partial and direct recovery of the electrical energy induced in the chemical dissolution reaction.
The method enables the storage of available electrical energy (e.g. during off-peak hours) and the recovery of the stored electrical energy (e.g. during peak hours) with high efficiency.

Claims (22)

1. Electrochemical device for storing electrical energy, comprising:
-a reactor (1) having:
o a side wall (2),
o a top wall (3),
o a bottom wall (5),
o an electrolyte inlet (7),
o an electrolyte outlet (8),
a plurality of electrodes E located in the reactor (1)xWherein x is an integer of 1 to n, the plurality of electrodes ExIn the form of a cone electrode and a frustum electrode and assembled in such a way that: the tapering part of each electrode is towards the top wall (3) or the bottom wall (5) of the reactor, the frustum electrode is in contact with the side wall (2) of the reactor (1), the apex of the cone electrode defines an axis through the open area of the frustum electrode, the cone and frustum electrodes are alternately arranged,
-wherein the cone electrode is spaced from the side wall (2) of the reactor (1) and the frustum electrode has an opening at the apex of the cone.
2. Electrochemical device (1) according to claim 1, characterized in that said plurality of electrodes ExHas an anode surface (9) and a cathode surface (10), the anode surface (9) and the cathode surface (10) being made of different materials.
3. Electrochemical device according to claim 2, characterized in that the anode surface (9) is covered by at least one metal wire wound to form turns defining a conical helix.
4. A device according to claim 3, characterized in that the turns of the conical helix engage to cover the anode surface (9).
5. A device according to claim 3, characterized in that said at least one wire is made of lead.
6. The device according to claim 5, characterized in that said anode surface is covered by a first metal wire and a second metal wire wound to form turns defining a conical helix, said first metal wire being made of lead and said second metal wire being made of tin.
7. According to claimThe device of claim 1, characterized in that said plurality of electrodes ExHaving the same surface.
8. Device according to claim 1, characterized in that the top wall (3) and the bottom wall (5) are conical in shape.
9. The device according to claim 8, characterized in that the cone electrode, the top wall (3) and the bottom wall (5) are substantially parallel to each other.
10. Electrochemical device according to claim 1, characterized in that:
-an electrolyte inlet (7) is located in the top wall (3),
-an electrolyte outlet (8) is located in a bottom part of the reactor, at a bottom wall (5) of the reactor and the plurality of electrodes EnIn the above-mentioned manner,
a plurality of electrodes E in which x is an odd integerxIs a cone electrode separated from the side wall (2) of the reactor (1),
a plurality of electrodes E in which x is an even integerxIs a frustum electrode having an opening at the apex of the cone and is in contact with the side wall (2) of the reactor (1),
to form a flow path for said electrolyte, said path going from an electrolyte inlet (7) to an electrolyte outlet (8), a plurality of electrodes E, in which x is an odd integer, being alternatedxAn electrode E arranged between the side wall (2) of the reactor (1) and in which x is an even integerxThrough an opening at the apex of the cone.
11. Electrochemical device (1) according to claim 1, characterized in that said plurality of electrodes ExAre electrically isolated from each other.
12. Device according to claim 1, characterized in that the top wall (3) forms an electrode and/or the bottom wall (5) forms an electrode.
13. Device according to claim 12, characterized in that the top wall (3) forms the cathode and/or the bottom wall (5) forms the anode.
14. Electrochemical device (1) according to claim 1, characterized in that it comprises an electrolyte tank connected to the electrolyte inlet (7) and the electrolyte outlet (8) of the reactor (1) to form a closed circuit.
15. Electrochemical device (1) according to claim 14, characterized in that said device comprises at least a second reactor comprising a plurality of electrodes, said two reactors being mounted in series, said two reactors being electrically connected and said second reactor being located between said first reactor and said electrolyte tank, the electrolyte outlet of said first reactor being connected to the electrolyte inlet of said second reactor and the electrolyte outlet of said second reactor being connected to said electrolyte tank.
16. Electrochemical device (1) according to claim 1, characterized in that said plurality of electrodes ExIs electrically connected to the negative terminal of the power supply and the plurality of electrodes ExIs connected to the positive terminal of the power supply.
17. Electrochemical device (1) according to claim 1, characterized in that said plurality of electrodes ExAnd the plurality of electrodes E and the first electrode (4)xIs connected to the electrical energy recovery system.
18. Method for storing electrical energy, comprising the following successive steps:
-providing an electrochemical device (1) according to claim 1,
-performing an introduction of an electrolyte to the electrochemical device (1), the electrolyte comprising metal ions,
-arranging said plurality of electrodes ExIs electrically connected to the negative terminal of the power supply and the plurality of electrodes ExIs electrically connected to the positive terminal of the power supply,
-providing electrical energy to reduce said metal ions at the first and second electrodes of said electrochemical device (1) to deposit metal and form an electrolyzable metal cell.
19. The method according to claim 18, characterized in that after the formation of said electrolyzable metal cell, said method comprises an operating phase of said electrolyzable metal cell, said operating phase comprising the dissolution of the deposited metal to generate electrical energy.
20. A method according to claim 19, characterized in that the first electrode (4) and the second electrode (6) are connected to an electric energy recovery system when the dissolution of the metal takes place.
21. The method according to claim 19, characterized in that the electrolyte used for forming said electrolyzable metal cell is reused for an operating phase of said electrolyzable metal cell.
22. The method according to claim 18, characterized in that said electrolyte is drained from the reactor (1) after the formation of said electrolyzable metal cell.
CN201680031378.5A 2015-06-30 2016-06-30 Electrochemical device for storing electrical energy Active CN107743664B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1556149 2015-06-30
FR1556149A FR3038456B1 (en) 2015-06-30 2015-06-30 ELECTROCHEMICAL DEVICE FOR STORING ELECTRIC ENERGY.
PCT/FR2016/051641 WO2017001786A1 (en) 2015-06-30 2016-06-30 Electrochemical device for storing electrical power

Publications (2)

Publication Number Publication Date
CN107743664A CN107743664A (en) 2018-02-27
CN107743664B true CN107743664B (en) 2021-01-15

Family

ID=54066081

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201680031378.5A Active CN107743664B (en) 2015-06-30 2016-06-30 Electrochemical device for storing electrical energy

Country Status (9)

Country Link
US (1) US20180123180A1 (en)
EP (1) EP3317913B1 (en)
JP (1) JP2018522366A (en)
KR (1) KR20180022650A (en)
CN (1) CN107743664B (en)
CA (1) CA2984468A1 (en)
FR (1) FR3038456B1 (en)
MA (1) MA42307B1 (en)
WO (1) WO2017001786A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200136160A1 (en) * 2018-10-24 2020-04-30 Gunes M. Ecer Simplified fuel cell system, apparatus, and process
FR3128589A1 (en) * 2021-10-22 2023-04-28 Ergosup Electrochemical system and process for the production of hydrogen by electrolysis of decoupled water, comprising a stage of deoxygenation of the electrolyte

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264263A1 (en) * 1986-10-14 1988-04-20 Comalco Aluminium, Ltd. Metal separation process
CN1074954A (en) * 1991-12-03 1993-08-04 帝国化学工业公司 Electrochemical cell
CN102395710A (en) * 2009-02-17 2012-03-28 麦卡利斯特技术有限责任公司 Electrolytic cell and method of use thereof
WO2012047188A1 (en) * 2009-08-27 2012-04-12 Mcalister Technologies, Llc Systems and methods for sustainable economic development through integrated full spectrum production of renewable energy
CN104380521A (en) * 2012-06-11 2015-02-25 巴斯夫欧洲公司 Electrode unit

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7976976B2 (en) * 2007-02-07 2011-07-12 Rosecreek Technologies Inc. Composite current collector
FR2948654B1 (en) * 2009-07-30 2015-01-16 Gerkaro COGENERATION OF ELECTRIC ENERGY AND HYDROGEN
FR3025055B1 (en) * 2014-08-19 2016-08-26 Jomi Leman ELECTROCHEMICAL DEVICE FOR STORING ELECTRIC ENERGY AND HYDROGEN PRODUCTION, AND PROCESS FOR PRODUCING HYDROGEN

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264263A1 (en) * 1986-10-14 1988-04-20 Comalco Aluminium, Ltd. Metal separation process
CN1074954A (en) * 1991-12-03 1993-08-04 帝国化学工业公司 Electrochemical cell
CN102395710A (en) * 2009-02-17 2012-03-28 麦卡利斯特技术有限责任公司 Electrolytic cell and method of use thereof
WO2012047188A1 (en) * 2009-08-27 2012-04-12 Mcalister Technologies, Llc Systems and methods for sustainable economic development through integrated full spectrum production of renewable energy
CN104380521A (en) * 2012-06-11 2015-02-25 巴斯夫欧洲公司 Electrode unit

Also Published As

Publication number Publication date
CN107743664A (en) 2018-02-27
US20180123180A1 (en) 2018-05-03
FR3038456B1 (en) 2019-10-18
MA42307A (en) 2018-05-09
KR20180022650A (en) 2018-03-06
EP3317913B1 (en) 2023-10-18
FR3038456A1 (en) 2017-01-06
CA2984468A1 (en) 2017-01-05
WO2017001786A1 (en) 2017-01-05
EP3317913A1 (en) 2018-05-09
MA42307B1 (en) 2023-12-29
JP2018522366A (en) 2018-08-09

Similar Documents

Publication Publication Date Title
JP6744306B2 (en) Electrochemical apparatus for storing electrical energy to produce hydrogen, and method for producing hydrogen
US7964301B2 (en) Dynamic accelerated reaction batteries utilizing Taylor Vortex Flows
TW200406944A (en) Fuel cell with embedded current collector
AU2016225020A1 (en) Electrochemical cell with bipolar faradaic membrane
EP2710655A1 (en) Zinc-air battery
JP6148472B2 (en) Metal-air secondary battery and electrode manufacturing method
JP2013222610A (en) Metal-air battery
CN107743664B (en) Electrochemical device for storing electrical energy
CN109537021A (en) A kind of preparation method of the titanium oxide for sodium-ion battery cathode/tin oxide composite membrane
KR102526924B1 (en) Operating method of regenerative bipolar membrane fuel cell and regenerative bipolar membrane fuel cell for the same
US10581127B2 (en) Anaerobic aluminum-water electrochemical cell
US10622690B2 (en) Anaerobic aluminum-water electrochemical cell
US10396418B2 (en) Anaerobic aluminum-water electrochemical cell
US10516195B2 (en) Anaerobic aluminum-water electrochemical cell
US10581128B2 (en) Anaerobic aluminum-water electrochemical cell
US10573944B2 (en) Anaerobic aluminum-water electrochemical cell
US10608307B2 (en) Anaerobic aluminum-water electrochemical cell
Bockelmann Investigation and prevention of anodic zinc passivation in alkaline zinc-air batteries
WO2022238584A1 (en) Metal-Air rechargeable flow battery
US20160322674A1 (en) Large-capacity electrical energy storage device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20231025

Address after: 2 Havelock Road, Javier Rock 2, # 04-07, Singapore

Patentee after: Global Energy Storage Co.,Ltd.

Address before: France West

Patentee before: Qiao Milaiman